Process for the dyeing of polyester textile materials

ABSTRACT

1. PROCESS FOR DYEING POLYESTER TEXTILE MATERIAL COMPRISING THE STEPS OF (1) IMMERSING THE POLYESTER TEXTILE MATERIAL IN A NONAQUEOUS DYEBATH CONSISTING ESSENTIALLY OF (A) WATER-IMMISCIBLE ORGANIC SOLVENT HAVING A BOILING POINT OF 40* C-150*C., (B) DISPERSE DYESTUFF; (C) WATER-SOLUBLE AROMATIC POLYSULPHONIC ACID ANIONIC DISPERSING AGENT; AND (D) CATIONIC DISPERSING AGENT, NON-IONIC DISPERING AGENT OR MIXTURE THEREOF; AND (2) LEAVING THE DYEING IN SAID DYEBATH UNTIL THE DESIRED DEPTH OF COLOR HAS BEEN OBTAINED .

3,846,070 PROCESS FOR THE DYEING F POLYESTER TEXTILE MATERIALS Werner Langmann and Robert Kuth, Cologne, Germany,

assignors to Bayer Aktiengesellschaft, Leverlrusen, Germany No Drawing. Filed Dec. 23, 1971, Ser. No. 211,727 Claims priority, application Germany, Dec. 23, 1970, P 20 63 330.1 Int. Cl. D0611 /06 US. Cl. 8-172 11 Claims ABSTRACT 015 THE DISCLOSURE The invention relates to a process for the dyeing of polyester textile materials with disperse dyestuffs; more particularly it concerns an exhaust process for the dyeing of polyester textile materials with disperse dyestuffs from organic water-immiscible solvents, which is characterised in that dyebaths of organic water-immiscible solvents are used which contain, besides the disperse dyestuffs, (a) water-soluble anionic dispersing agents and (b) cationic and/or non-ionic tensides.

Suitable organic water-immiscible solvents are solvents the boiling point of which lies between 40' and 150 C., e.g. aromatic hydrocarbons such as toluene and xylene; aliphatic halogenated hydrocarbons, especially chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, t-etrachloroethane, dichloropropane, chlorobutane and dichlorobutane; aliphatic fluorinated and fiuoro-chlorinated hydrocarbons such as perfiuoro-n-hexane, 1,2,2- trifluoro-trichloroethane, and trifluoro-pentachloropropane; aromatic chlorinated and fiuorinated hydrocarbons such as chlorobenzene, fluorobenzene, chlorotoluene and benzo-trifiuoride.

Tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane and 1,1,1-trichloropropane have proved particularly satisfactory. Mixtures of these solvents can also be used.

The disperse dyestuffs used for the dyeing process according to the invention are disperse dyestuffs conventionally used for dyeing polyesters and cellulose esters, such as are described, for example, in Colour Index, vol. 1, pp. 1655-1742, 2nd edition (1956). It must be emphasized that the term disperse dyestuffs also refers to optical brightening agents. Disperse brightening agents of this 'kind are described, for example, in H. Hefti, Textilveredelung 4 (1969), Pp 94 seq., and in British patent specification No. 1,113,918.

The water-soluble anionic dispersing agents to be used according to the invention are primarily the known dispersing agents derived from aromatic sulphonic acids, for example, the condensation products of naphthalene-sulphonic acid with formaldehyde, or of cresol, B-naphtholsulphonic acid and formaldehyde; or polystyrene-sulphonic acid, or the disulphonate of heptadecyl benzimidazole; furthermore, the known dispersing agents derived from sulphite cellulose waste liquor and its reaction products with aniline. These dispersing agents are described, for example, in Lindner, Tenside-Textilhilfsmittel-Waschrohstoffer, 2nd edition (1964), vol. I, pp. 767, 809, vol. II, p. 1585.

United States Patent 0 Patented Nov. 5, 1974 "ice As cationic tensides there are advantageously used amines of the formula in which R stands for a C C -alkyl or C C -alkenyl radical;

and

R and R independently of one another, mean hydrogen; a c -C -alkyl or C -C -alkenyl group; or a group of the formula -(C H O) R Where R stands for hydrogen, a C C -alkyl, a phenyl or a C -C -alkyl phenyl radical, and n stands for a number from 1 to 10,

with the proviso that at least one of the radicals R, R or R contains an alkyl chain with at least 5 carbon atoms and that the total number of (C H O) units in the amine molecule is not higher than 10.

Examples of amines of the formula (I) are, for example: primary amines, such as pentylamine, iso-pentylamine, octylamine, 2-ethylhexylamine, decylamine, d0- decylamine, stearylamine, oleylamine, eicosylamine, docosylamine; secondary amines, such as N-methyl-pentylamine, N-butyl-Z-ethylhexylamine, N-methyl-dodecylamine, N-methyl-stearylamine, N-ethyl-oleylamine, N- methyldocosylamine; tertiary amines, such as N,N-dimethyl-pentylamine, N,N dimethyl-Z-ethylhexylamine, N,N bis (B-hydroxyethyl)-stearylamine, the reaction products of one mol stearylamine with 5 mol ethylene oxide, of one mol oleylamine with 8 mol ethylene oxide, of one mol docosylamine with 10 mol ethylene oxide, and N,N-dimethyl-2-[2 (4 dodecyl-phenoxy)-ethoxy]- ethylamine.

The amines of the formula (I) may also be present as quarternised compounds; representatives are, for example: N,N-dimethyl-N-benZyl-stearyl ammonium chloride, N,N,N-trimethyl-N-dodecyl ammonium metasulphate, N,N-dimethyl-N-dodecyl-N-benzyl ammonium chloride, N,N-dimethyl-N,N-distearyl ammonium chloride and N,N-dimethyl-N-benzyl-N 2 [2-(4-isooctylphenoxy) ethoxy]-ethyl ammonium chloride.

The cationic tensides to be used according to the invention must be soluble or at least dispersible in the organic solvents. The quaternisation products frequently do not meet this requirement. However, when they are mixed with the non-ionic tensides described below, then mixtures are obtained which are soluble or dispersible in the organic solvents and are eminently suitable as components (b) in the mixtures of auxiliaries to be used according to the invention.

As non-ionic tensides in the mixtures of auxiliaries to be used according to the invention, there may be used the known non-ionic tensides, provided they are soluble or dispersible in the organic solvents or yield with the cationic tensides mixtures which are soluble or dispersible in organic solvents. The reaction products of ethylene oxide with fatty alcohols, fatty acids, fatty amines, alkylphenols and fatty acid amides have mainly proved satisfactory; furthermore, carboxylic acid amides which are free from amino groups, e.g. fatty acid monoor dialkylamides or fatty acid monoand dialkanolamides.

The quantitative proportions between the dyestuffs and the mixtures of auxiliaries to be used according to the invention may vary within wide limits; they depend on the type of dyestulf and can easily be established in each case by preliminary experiments. In general, 0.3 to 3 parts of the water-soluble anionic dispersing agent and 0.5 to 4 parts of non-ionic and/or cationic tenside are used for every part of dyestuif.

It can be advantageous to add to the mixture of auxiliaries small amounts of lower alcohols, e.g. ethanol or butanol, and/ or water; however, the quantitative proportion of these additives should not exceed the total amount of auxiliaries (a) and (b).

The dyebaths to be used according to the invention are advantageously prepared by first pasting or grinding the dyestuff with the anionic dispersing agent; subsequently adding to the resultant paste the remaining auxiliaries together with small amounts of the solvent used for dyeing; and working up all the components together to form a homogeneous mixture. The latter is subsequently diluted to the desired concentration by the addition of more solvent.

Dyeing of the polyester textile materials in the baths so obtained is carried out in known manner by introducing the textile materials into the dyebath at to 60 C., heating the bath to 100 to 120 C., and dyeing at the same temperature until the desired depth of colour has been attained. The dyed textile material is then rinsed with fresh solvent, first hot, then cold, and subsequently dried.

If the dyebaths to be used according to the invention are not prepared with the use of pure disperse dyestuffs, but with commercial disperse dyestuffs, i.e. those formulated with anionic dispersing agents, these dyestuffs may immediately be worked up together with the nonionic and/or cationic tensides to form the homogeneous mixture which can be diluted with the organic solvents.

With the aid of the process according to the invention a there are obtained remarkably level and deep dyeings on textile materials of poly-esters. The polyesters primarily comprise polyethylene terephthalates, polycyclohexane-dimethylene terephthalate, or polycarbonates of 2,2-bis-(phyd'roxyphenyl)-propane, and cellulose triacetate. The materials may be present in various stages of processing, e.g. as filaments, yarn, fabrics, knitted fabrics, or ready-made goods.

The advantage of the process according to the invention over the known processes for the dyeing of polyester materials from organic water-immiscible solvents consists in a higher exhaustion of the bath within a shorter period of time that is to say that a higher dyeing speed is achieved. Furthermore, the process according to the invention offers the advantage of permitting of the use of the commercial disperse dyestuffs formulated for dyeing from aqueous baths and is not subject to the use of pure dyestuffs.

It is known that water-soluble anionic dispersing agents are not suitable for dispensing non-ionic dyestuffs in organic water-immiscible solvents because they are insoluble in these solvents. It is further known that although nonionic and/or cationic tensides can be used as auxiliaries for dyeing polyester materials from organic water-immis cible solvents, their effectiveness in furthering the drawing of the dyestuff is unsatisfactory. It was therefore surprising that the combination of an auxiliary which cannot be used as such for the dyeing from organic waterirnmiscible solvents, with auxiliaries whose effectiveness in this dyeing process is unsatisfactory should lead to a mixture of auxiliaries enabling very level dyeings to be obtained not only with excellent dyestuff yields but also in shorter dyeing times.

The parts used in the examples are parts by weight.

EXAMPLE 1 1 part of the dyestuff of the formula OH O OH is ground in a ball mill with 1 part of the sodium salt of formaldehyde (prepared according to Can. patent speci- 4 the reaction product of B-naphthalene-sulphonic acid and fication No. 347,865) and 1 part of water. 3 parts of this mixture are stirred with 1 part of the emulsifier mixture described below in 10 parts perchloroethylene and then diluted with 1600 parts of the same solvent.

A fabric of polyethylene glycol terephthalate is introduced in a liquor ratio of 1:20 into the dyebath so prepared. The dyebath is heated in a closed dyeing vessel to 120 C. and this temperature is maintained for 1 hour. The fabric is subsequently rinsed with warm and then with cold perchloroethylene, and then dried. A deep and level blue dyeing of the fabric is obtained.

The emulsifier mixture used above had been prepared by mixing 1 part oleic acid ethanolamide, 1 part of the reaction product of 20 mol ethylene oxide with 1 mol oleyl alcohol and 1 part of water.

The quantity of dyestuff absorbed by the polyester fabric amounts to 5.2 mg./ g. fabric.

When dyeing was carried out in a bath containing only the emulsifier mixture described above, but not the watersoluble anionic dispering agent, then the quantity of dyestuif absorbed was 4.0 mg./g. fabric; when a bath was used which contained no auxiliary at all, the absorption amounted to 3.1 mg. dyestuff/ g. fabric.

When the water-soluble anionic dispersing agent used above was replaced with the same amount of a 1:1:1 reaction product of cresol, B-naphthol-sulphonic acid and formaldehyde, and the above emulsifier mixture was replaced with 8 parts N,N dimethyl-N-dodecyl-N-benzyl ammonium chloride, an equally satisfactory dyeing was obtained.

An equally satisfactory dyeing was also obtained on a fabric of cellulose triacetate.

EXAMPLE 2 1 part of the dyestuff of the formula H OH 0 is stirred with 2 parts of the reaction product of 2 mol naphthalene-sulphonic acid and 1 mol formaldehyde, and with 8 parts dodecylamine and 10 parts perchloroethylene. The mixture is subsequently diluted with 1600 parts of the solvent.

50 parts of a fabric of polyethylene glycol terephthalate are introduced at room temperature into the dyebath so prepared. The bath is heated to C. within 30 minutes and the same temperature is maintained for 30 minutes. The fabric is subsequently rinsed with pure solvent, and then dried. A level clear blue dyeing is obtained.

An equally satisfactory level blue dyeing was also obtained within the same dyeing time, when the dodecylamine was replaced with the same amount of a mixture of 6 parts -N,N distearyl-N,N-dimethyl ammonium chloride, 1 part isopropanol, and 1 part of water.

EXAMPLE 3 1 part of the dyestuff of the formula CH7CHCN is ground in a ball mill with 2 parts of a product prepared from a sulphite-cellulose waste liquor product and aniline, and with 1 part isobutanol. 5 parts of this mixture are stirred with 2 parts nonylphenol decaethylene glycol ether and 20 parts perchloroethylene, and diluted with a further 800 parts perchloroethylene.

50 parts of a fabric of polyethylene glycol terephthalate are dyed in the dyebath so prepared, as described in Example 1. A level deep scarlet-red dyeing is obtained on the fabric.

An equally satisfactory dyeing was obtained on a knitted fabric of cellulose triacetate.

EXAMPLE 4 6 parts of the dyestuff of the formula CH CH;4O oooHi N CHz-CHz-O C CH3 are worked up with 5 parts of the Water-soluble dispersing agent described in Example 3, 5 parts of the 1:1:1 reaction product of cresol, ,B-naphthalene-sulphonic acid and formaldehyde (sodium salt) and 4 parts of water to form a paste. 7 parts of this paste are stirred with 10 parts of the reaction product of 10 mol ethylene oxide and 1 mol hexadecylamine, 3 parts isobutanol and 40 parts perchloroethylene, and subsequently diluted with 1600 parts of the solvent.

Dyeing is carried out with this dyebath as described in Example 1. A brilliant red dyeing is obtained on the polyester fabric.

EXAMPLE 5 1 part of the dyestuff of the formula is ground in a ball mill With 2 parts of the sodium salt of lignin-sulphonic acid and 1 part isobutanol. 5 parts of this mixture are diluted with 2 parts hexadecylamine and parts perchloroethylene, and subsequently diluted with a further 800 parts perchloroethylene.

50 parts of polyester fabric are dyed in the dyebath so prepared, as described in Example 1. A level brillant yellow dyeing is obtained on the polyester fabric.

What is claimed is:

1. Process for dyeing polyester textile material comprising the steps of (1) immersing the polyester textile material in a nonaqueous dyebath consisting essentially of (a) water-immiscible organic solvent having a boiling point of 40 C.150 C.;

(b) disperse dyestnif;

(c) water-soluble aromatic polysulphonic acid anionic dispersing agent; and

(d) cationic dispersing agent, non-ionic dispersing agent or mixture thereof; and

(2) leaving the dyeing in said dyebath until the desired depth of color has been obtained.

2. The process of Claim 1 in which said non-aqueous dyebath contains in addition (e) a C C -lower alcohol in a small amount not exceeding the total amount of (c) and (d).

3. The process of Claim 1 in which (d) consists of a cationic dispersing agent.

4. The process of Claim 1 in which (c) is condensation product of naphthalene-sulphonic acid, cresol or B-naphthol-sulphonic acid and formaldehyde; polystyrene-sulphonic acid; products derived from sulphite cellulose waste liquor or their reaction products with aniline.

5. Process of Claim 1 in which the ratio of the amount of (c) water-soluble anionic dispersing agent and (d) cationic and/ or non-ionic dispersing agent to the amount of (b) disperse dyestuff, is as 0.3-3:0.5-4:1.

6. Process of Claim 1 in which the cationic dispersing agent (d) is an amine or the quaternization product thereof said amine having the formula in which R is C -C -alkyl or C -C -alkenyl; R and R independently of one another, are hydrogen; C C alkyl; C C -alkenyl; or --(C H O) R where R is hydrogen, C C -alkyl, phenyl or C C -alkylphenyl; and n is a number from 1 to 10; with the proviso that at least one of the radicals R, R or R contains an alkyl chain with at least 5 carbon atoms, and that the total number of (C H O)- units in the amine molecule is not greater than 10.

7. Process of Claim 1 in which the non-ionic dispersing agent (d) is the reaction product of ethylene oxide with fatty alcohol, fatty acid, fatty amine, alkylphenol or fatty acid amide; or amino group-free carboxylic acid amides; which are soluble or dispersible, or are soluble or disersible in mixture with the cationic dispersing agent, in the organic solvents.

8. The process of Claim 1 in which said water-immiscible solvent is chlorinated, fluorinated, or chlorofluorinated aliphatic hydrocarbon having a boiling point of 40 C.150 C.

9. The process of Claim 1 is conducted by immersing the polyester textile material in said dyebath at 20 C. 60 C., heating the dyebath to C. C. and maintaining the dyebath at 100 C.-120 C. until the desired depth of color has been achieved.

10. The process of Claim 1 in which the material subjected to steps (1) and (2) is subsequently (3) rinsed in organic water-immiscible organic solvent;

and

(4) dried.

11. Polyester textile materials dyed by the process of Claim 1.

References Cited UNITED STATES PATENTS 2,828,180 3/1958 Sertorio 8-62 3,057,674 10/1962 Musser et al. 8-83 FOREIGN PATENTS 1,192,984 5/ 1970 Great Britain 8174 737,118 4/1970 Germany 8-174 THOMAS J. HERBERT, JR., Primary Examiner US. Cl. X.R. 8-83, 94, 173, 174 

1. PROCESS FOR DYEING POLYESTER TEXTILE MATERIAL COMPRISING THE STEPS OF (1) IMMERSING THE POLYESTER TEXTILE MATERIAL IN A NONAQUEOUS DYEBATH CONSISTING ESSENTIALLY OF (A) WATER-IMMISCIBLE ORGANIC SOLVENT HAVING A BOILING POINT OF 40* C-150*C., (B) DISPERSE DYESTUFF; (C) WATER-SOLUBLE AROMATIC POLYSULPHONIC ACID ANIONIC DISPERSING AGENT; AND (D) CATIONIC DISPERSING AGENT, NON-IONIC DISPERING AGENT OR MIXTURE THEREOF; AND (2) LEAVING THE DYEING IN SAID DYEBATH UNTIL THE DESIRED DEPTH OF COLOR HAS BEEN OBTAINED . 